Trihalo-tetrahydronorpolycyclo-pentadienes



Patented Au 14, 1945 TBIHALO -TETRAEYDRONORPOLYCYCLO- PENTADIENES Herman A. Brnson, Philadelphia, Pa., asaignor to The Delirious Products 8: Chemical Company, Philadelphia, 'Pa., a corporation of Delaware No Drawing. Application February 20, 1943, Serial No. 476,644

10 Claims.

This invention relates to trihalo-tetrahydronorpolycyclopentadienes and a method for their preparation.

It is known that dicyclopentadieue reacts with halogens to form extremely unstable addition products which split 01! hydrogen halide and resinify when warmed, and which are unstable even at ice-bath temperature. (Roscoe, Liebig's Annalen der Chemie, 232, 349 (1886).)

However, in accordancewith the disclosure of th present application, which is a continuationin-part o1 copending application Serial No. 434,262, filed March 11, 1942, well-defined, relatively stable trihalogen derivatives are obtained from dicyclopentadiene, tricyclopentadiene, and higher polycyclopentadienes having two double bonds per molecule by first adding a member of the group consisting of hydrogen chloride, hydrogen bromide, or hydrogen iodide to one of the double bonds of the polycyclopentadiene molecule, to form an addition-rearrangement product having the norpolycyclopentadiene ring system as hereinafter more fully described, and subsequently reacting the norpolycyclopentadiene monohydrohalide thus formed with a halogen having an atomic weight greater than that of fluorine,

whereby the remaining double bond becomes saturated by taking up two halogen atoms.

Typical polycyclopentadienes which can be used for the purpose of this invention are, for example, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene, homologues and isomers thereof containing two double bonds per molecule. Such polymers are crystalline solids obtainable by heating cyclopentadiene at 150-200 C. in a closed vessel. They possess the generaltormula:

. acids is employed, that the addition occurs on the double bond of the cycle having the endomethylene bridge, and that a simultaneous molecular rearrangement takes place in this ring to form a hitherto unknown class of cyclic compounds having the norpolycyclopeutadiene ring system as more fully described in copending application Serial No. 476,641, filed February 20, 1942.

The reaction between dlcyclopentadiene and hydrogen halide in the presence of water is generically shown by the equation:

c l 1 B,

wherein 03H is a propenylene group which conjointly with the adjoining carbon atoms forms a cyclopenteno group. The cyclopenteno group may have thestructure:

on, -cn--cn C{ \CH or all H, cs

Tricyclopentsdionc K Nortricyclopeutadiens munohydrohalidc Similarly, tetracyclopentadiene and pentacyclopentadiene add hydrogen halides to form norpolycyclopentadiene monohydrohalides.

The addition of hydrogen chloride, hydrogen bromide, or hydrogen iodide to dicyclopentadiene or higher polycyclopen-tadienes takes place readily at 50-110 C. in the presence of water to yield the norpolycyclopentadiene monohydrohalides having a terminal flve-membered cycle containing a double bond. This addition is most conveniently performed with ordinary concentrated aqueous hydrochloric acid (35%), h'ydrobromic acid (48%) or hydriodic acid (47%) but both stronger and weaker solutions of the hydrogen halides. may be used. The reaction takes place in, a few hours under the influence or rapid stirring.

The addition of chlorine or bromine to the above norpolycyciopentadiene monohydrohalides takes place with great ease even at C. and is complete in a short time at 20-25 C. In order to inhibit undue substitution it is advantageous to employ an inert solvent, such as, for example, carbon tetrachloride, as a reaction medium and to maintain the temperature below 30 C. although both higher and lower temperatures may be used Iodine adds very slowly to the double bond and is advantageously employed as iodine monochloride or iodine monobromide. As a result of these reactions, dicyclopentadiene, for example, yields trihalo tetrahydronordlcyclopentadienes having the formula:

"a c I L c CH-Y H: JL n-z' Tricyclopentadiene in the same manner yields trihalo-tetrahydronortricyclopentadienes having the formula:

. cation. They may find application as plasticizers for polyvinyl chloride, synthetic rubber, rubber hydrochloride and other types of plastics.- They also possess insecticidal proper-ties and are useful intermediates for the preparation of the corresponding glycols, amines, esters, nitriles, thiocyanates and many other types of organic compounds. They may be added to lubricating oils to improve their oiliness and load-bearing properties.

The following examples illustrate this invention. The parts given are by weight.

Example 1 Chlorine was passed intoa solution of 84 parts of nordicyclopentadiene monohydrochloride and 84 parts of carbon tetrachloride at -20 C. until the gain in weight amounted to 50 parts. The product was washed with water, then with dilute soda solution and finally with water. The dried oil was then distilled inyacuo after evaporation of tilled at 143-153 C./2 mm. and upon redistiliation boiled at 175.-180 C./11 mm. The yield was 98 parts,

The nordicyclopentadiene monohydrochloride used boils at 100-102 C./11 mm.

Example 2 To a solution of 84 parts of nordicyclopentadiene monohydrochloride in 84 parts of carbon tetrachloride 80 parts of bromine was added gradually during one hour while the reaction mixture was stirred and cooled to 5 C. The product was washed with water, then dilute soda solution, and finally with water, and evaporated to remove the solvent. The residual oil weighing 159 parts was distilled in vacuo. The dibromo-monochloro-tetrahydronordicyclopentadiene distilled at 165-1'73 C./2 mm. as a pale yellow viscous liquid in a yield of 138 parts. Upon redistiiiation it boiled at 191-194 C./11 mm.

Example 3 To a solution of v one molecular equivalent of nordicyclopentadiene monohydriodide in an equal volume of carbon tetrachloride cooled to 0 C. one mol of chlorine was introduced. The product was washed with water, dried, and the solvent removed by evaporation. The oily residue consisted essentially of dichlor0-i0dotetrahydronordicyclopentadiene a a 0ft c CH-Cl OH: I- H L 11-01 The nordicyclopentadiene monohydriodide used boils at -132' C./11 mm.

Example 4 diiistilled at 156 C./3 mm. as a pa e yellow thick 0 The .nordicyclopentadiene monohydrobromide used boils at 113-114 C./11 mm.

Emmple To a solution or 42.8 parts of nordieyclopentadiene monohydrobromide in 50 parts of carbon tetrachloride, cooled to C. and stirred, there was CH-Br (a) Into a solution of 235 parts or nortricyclopentadiene monohydrochloride in 250 parts of carbon tetrachloride cooled to 10 C. chlorine was introduced until the gain in weight was 70 parts. Th solvent was removed by evaporation in vacuo at 100 C. The residual oil consisted essentially of trichlorotetrahydronortricyclopentadiene having the formula The nortricyclopentadiene monohydrochloride used is a pale yellow liquid boiling at 175 C./11 mm.

(b) By using 160 parts of bromine in the above reaction in place of the chlorine, the corresponding chloro-dibromotetrahydronortricyclopentadiene having the formula on OH on, c{i c CHBr H] H! 01- H/ H -Br was obtained as a thick oil.

Emmple 7 500 parts of dicyclopentadiene is heated in a sealed vessel at 180 C. for 8 hours. The waxy solid obtained, consisting essentially oitricyclo- C a H wherein X, Y, and Z represent one or more kinds of halogen atoms having atomic weights greater than 19 and n is a number from zero to a small whole number.

While in the above examples pure or relatively pure polycyclopentadlene or mixtures thereof are shown for purposes of illustration, there may also be used as a source of polycyclopentadienes having two double bonds per molecule mixtures of hydrocarbons containing 5% or more or these polycyclopentadienes. Such mixtures are obtained from various processes involving thermal cracking of petroleum oils. The reaction of the polycyclopentadienes as shown aboveprovides a new means of separating some of the components of mixtures and gives a new utility thereto.

I claim:

1. A trihalotetrahydronorpolyeyclopentadiene, all halogen atoms of which have atomic weights above nineteen. said product being obtained by adding in the presence of water a hydrohalide to a polycyclopentadiene having two double bonds and one to four endomethylene cycles per molecule, with subsequent rearrangement to form a halodihydronorpolycyclopentadiene having a ter. minal cyclopenteno group, and adding at a temperature below about 30 C. two halogen atoms to saturate said cyclopenteno group.

2. A trihalotetrahydronordicyclopentadiene, all

halogen atoms of which have atomic weights above pentadiene, tetracyclopentadiene, pentacyclopennineteen, said product being obtained by adding a hydrohalide to dicyclopentadiene in the presence of water, with subsequent rearrangement to form a halodihydronordicyclopentadiene having a terminal cyclopenteno group, and adding at a temperature below about 30 0. two halogen atoms to saturate said cyclopenteno group.

3. A trichlorotetrahydronordicyclopentadiene, a compound obtained by adding hydrogen chloride to dicyclopentadiene in the presence or water, with subsequent rearrangement to form chlorodihydronordicyclopentadiene having a terminal cyclopenteno group, and adding at a temperature below about 30 C. chlorine to saturate said cyclopenteno group.

4. Bromodichlorotetrahydronordicyclopentadiene, a compound obtained by adding hydrogen bromide to dicyclopentadiene in the presence of water, with subsequent rearrangement to form bromodihydronordicyclopentadiene having a terminal cyclopenteno group, and adding at a temperature below about 30 C. chlorine to saturate said cyclopenteno group.

5. Chlorodibromotetrahydronordicyclopentadiene, a compound obtained by adding hydrogen chloride to dicyclopentadiene in the presence of water, with subsequent rearrangement to form chlorodihydronordicyclopentadiene having a terof the tetrahydronorpoiycyclopentadienes may 7 minal y p nten Gro p. and adding at a temperature below about 80 C. bromine to saturate saidcyclopenteno group.

6. A method for preparing trihalotetrahydronorpolycyclopentadienes which comprises reacting by addition in the presence of water a crystalline polycyclopentadiene having two double bonds and one to four endomethylene cycles per molecule and a hydrogen halide, the halogen of which has an atomic weight above nineteen, to yield an addition product, forming by rearrangement of said addition product a halodihydronorpolycyclopentadiene having a terminal cyclopenteno group, and adding to the cyclopenteno group of said halodihydronorpolycyclopentadiene at a temperature below about 30 C. two equivalents of halogen of atomic weight greater than nineteen.

'7. A method for preparing trihalotetrahydronordicyclopentadienes which comprises reacting by addition in the presence of water dicyclopentadiene and a hydrogen halide, the halogen of which has an atomic weight above nineteen,

to yield an addition product, forming by rearrangement of said addition product a halodihydronordicyclopentadiene having a terminal cyclopenteno group, and adding to the cyclopenteno group of said halodihydronordicyciopentadiene at a temperature below about 30 C. two equivalents oi halogen of atomic weight greater than nineteen.

8. A method for preparing trichlorotetrahydronordicyclopentadiene which comprises reactin by addition in the presence of water hydrogen chloride and dicyclopentadiene, to yield an ad: dition product which rearranges to chlorodihydronordicyclopentadiene having a terminal cyclopenteno group, and adding to the cyclopenteno group of said chlorodihydronordicyclopentadiene at a temperature below about C. two equivalents of chlorine.

9. A method preparing bromodichlorotetrahydronordicyclopentadiene which comprises reacting by addition in the presence oi water hydrogen bromide and dicyclopentadiene, to yield an addition product which rearranges to bromodihydronordicyclopentadiene having a terminal cyclopenteno group, and adding to the cyclopenteno group of said bromodihydronordicyclopentadiene at a temperature below about 30 C. two equivalents of chlorine.

10. A method of preparing chlorodibroxnotetrahydronordicyclopentadiene which comprises reacting by addition in the presence of water hydrogen chloride and dicyclopentadiene, to yield an addition product which rearranges to chlorodihydronordicyclopentadiene having a terminal cyclopenteno group, and adding to the cyclopenteno group of said chlorodihydronordicyclopentadiene at a temperature below about 30 C. two equivalents of bromine.

HERMAN A. BRUSON. 

